CN117637974A - Three-dimensional composite zinc cathode and preparation method and application thereof - Google Patents
Three-dimensional composite zinc cathode and preparation method and application thereof Download PDFInfo
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- CN117637974A CN117637974A CN202210966346.1A CN202210966346A CN117637974A CN 117637974 A CN117637974 A CN 117637974A CN 202210966346 A CN202210966346 A CN 202210966346A CN 117637974 A CN117637974 A CN 117637974A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 239000011701 zinc Substances 0.000 title claims abstract description 172
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 171
- 239000011165 3D composite Substances 0.000 title abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 48
- 238000004070 electrodeposition Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 84
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 60
- 229910052802 copper Inorganic materials 0.000 claims description 59
- 239000010949 copper Substances 0.000 claims description 59
- 238000007747 plating Methods 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 15
- 229960001763 zinc sulfate Drugs 0.000 claims description 15
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- 239000002344 surface layer Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 37
- 238000000151 deposition Methods 0.000 abstract description 30
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000005137 deposition process Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 230000008021 deposition Effects 0.000 description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 description 12
- 235000011152 sodium sulphate Nutrition 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 210000001787 dendrite Anatomy 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method and application of a three-dimensional composite zinc anode. Through electrodeposition technology, a zinc layer is pre-deposited on the surface of a three-dimensional substrate with a porous structure, and the three-dimensional composite material can be directly used as a zinc anode and applied to a water-based zinc-based battery. The morphology and crystal face orientation of the pre-deposited layer are successfully regulated and controlled by regulating and controlling the current density in the pre-deposition process. The invention has simple process and high preparation speed and meets the green chemical requirements. When used as the negative electrode of the water-based zinc ion battery, the zinc foil has obviously improved cycle stability and rate capability compared with commercial zinc foil. The pre-deposition method developed by the invention has been proved to be capable of preparing the zinc layer with specific morphology and crystal face orientation on the surface of the three-dimensional substrate, so that the zinc cathode shows excellent cycle and rate capability, and is a zinc cathode surface modification technology with application prospect. The three-dimensional composite material with the zinc layer with specific surface characteristics deposited on the surface of the three-dimensional porous substrate, developed by the invention, is a zinc negative electrode capable of realizing excellent cycle and rate performance, and can be widely applied to large-scale, mobile portable, miniature or flexible wearable zinc-based batteries based on the zinc negative electrode.
Description
Technical Field
The invention belongs to the technical field of nano materials and electrochemistry, and particularly relates to a three-dimensional composite zinc anode, a preparation method and application thereof, wherein a zinc layer with specific surface characteristics is pre-deposited on the surface of a three-dimensional substrate with a porous structure, and the three-dimensional composite material can be directly used as a zinc anode for a zinc-based battery, such as a water-based zinc ion battery.
Background
With the increasing demand for energy and the increasing global environmental problems, the development of clean and renewable energy is imperative. Lithium ion batteries have been widely used in electric automobiles and mobile electronic devices. However, the problems of insufficient lithium reserves, high price, poor safety, etc. limit the further development of lithium ion batteries. In recent years, aqueous zinc-based batteries based on zinc metal negative electrodes, such as zinc ion batteries, zinc-air batteries, zinc-based flow batteries, and the like, have been found to be low in cost, environmentally friendly due to high zinc storage, and high specific capacity of zinc metal (-820 mA h g) -1 ) And have received a great deal of attention. However, uneven electric field distribution on the surface of commercial zinc foil causes uneven zinc deposition/stripping process and dendrite growth, continuous growth of zinc dendrite may puncture the separator, which may cause short circuit of the battery, and in addition commercial zinc foil may undergo side reaction in aqueous electrolyte, resulting in low coulombic efficiency during cycling. So when commercial zinc foil is used for the negative electrode of the aqueous zinc-based battery, the growth of zinc dendrites and side reactions can seriously affect the cycling stability of the zinc negative electrode.
The repeated deposition/stripping process of the zinc anode is highly dependent on the surface properties of the zinc anode such as morphology and crystal plane orientation. Recently, the oxford university team adopts a block single crystal zinc sheet with a single (002) crystal face as a zinc metal negative electrode, so that highly reversible zinc metal deposition/stripping is realized, and the cycle and rate performance of the battery are greatly improved. The (002) crystal face and the surface of the zinc sheet with compact surface are key to realizing highly reversible zinc deposition/stripping by promoting the uniform distribution of the electric field on the surface of the zinc sheet, adjusting the nucleation growth process of zinc metal and reducing side reaction.
The present invention is to pre-deposit a zinc layer having a dense sheet-like stacked surface property mainly oriented with (002) crystal planes on a copper mesh having a three-dimensional porous structure by a controlled current electrodeposition method for the first time. When the three-dimensional composite material is used as a zinc anode, the surface property of the pre-deposited zinc layer reduces dendrites and side reactions by promoting the uniform distribution of an electric field on the surface of the zinc anode, and improves the cycle reversibility of the zinc anode. The electrodeposition method can be popularized to the controllable zinc metal pre-deposition of other three-dimensional porous current collectors, and a pre-deposited zinc layer with (002) crystal face orientation and compact flaky stacking surface property is prepared.
Further popularizing, depositing a zinc layer with (002) crystal face orientation and compact flaky stacking surface property on the surface of the three-dimensional substrate with a porous structure by any pre-deposition method, wherein the three-dimensional composite material can be used as a zinc cathode to realize reversible zinc metal deposition/stripping, thereby improving the cycle and rate capability of the battery.
Therefore, the invention develops the three-dimensional composite material with the zinc layer with specific surface characteristics deposited on the surface of the three-dimensional porous substrate, which is the zinc negative electrode capable of realizing excellent cycle and rate performance, and can be widely applied to large-scale, mobile portable, miniature or flexible wearable zinc-based batteries based on the zinc negative electrode.
Disclosure of Invention
Aiming at the technical problems of the zinc metal negative electrode in the prior art, the invention develops a brand-new three-dimensional composite zinc negative electrode, and a preparation method and application thereof. The three-dimensional composite material can be directly used as a zinc cathode for a zinc-based battery, such as a water-based zinc ion battery, by pre-depositing a zinc layer with specific surface characteristics on the surface of a three-dimensional substrate with a porous structure. The preparation method has simple process and high preparation speed, meets the green chemical requirement, and the pre-deposited zinc cathode assembled into the water-based zinc ion battery shows excellent cycle and rate performance, thus being a zinc cathode with application prospect.
The technical scheme provided by the invention aiming at the technical problems of the zinc metal cathode is as follows: a zinc metal layer with compact flaky stacking and (002) crystal face orientation is pre-deposited on the surface of a three-dimensional substrate, wherein the zinc layer is pre-deposited on the surface of a copper mesh with a three-dimensional porous structure by a controlled current electrodeposition method, and the pre-deposited layer has the surface characteristics of compact flaky stacking and (002) crystal face orientation, and is fully covered and uniformly distributed on the surface of the copper mesh. The "(002) crystal plane orientation" surface characteristics referred to in this application all refer to the (002) crystal plane orientation as the main.
Specifically, the invention provides a battery cathode which comprises a three-dimensional substrate and a zinc metal surface layer attached to the three-dimensional substrate, and is characterized in that the three-dimensional substrate has a three-dimensional porous structure, and the surface layer is a zinc layer which is mainly oriented by a (002) crystal face and is densely stacked in a flake shape.
As a characterization of the (002) crystal plane orientation, the X-ray diffraction pattern of the zinc layer has strong characteristic peaks at 2θ=35 to 37 degrees.
According to the present invention, the foregoing zinc layer may be formed by an electrodeposition method. The three-dimensional substrate may be a copper mesh.
According to the present invention, the battery anode may be a zinc metal anode for a zinc-based battery.
The invention also provides a preparation method of the battery cathode, wherein a three-dimensional substrate is used as a working electrode, and the preparation method is characterized in that the surface layer is formed on the three-dimensional substrate by an electrodeposition method of controlling current.
The preparation process according to the invention, in which the electrodeposited current density is preferably from 10 to 300mA cm -2 。
According to the preparation method of the invention, the three-dimensional substrate can be a conductive three-dimensional current collector. The three-dimensional current collector may be made of a material selected from the group consisting of: metals, alloys, carbon materials, carbon composites.
The preparation method according to the invention, wherein the plating solution used may comprise a zinc salt selected from the group consisting of: zinc sulfate, zinc chloride, zinc trifluoromethane sulfonate, zinc bromide, zinc acetate.
The preparation method according to the invention, wherein the electroplating bath used may further comprise additives selected from the group consisting of: sulfuric acid, boric acid, indium sulfate, phosphoric acid.
A preferred embodiment of the production method according to the present invention, wherein the three-dimensional substrate is a copper mesh, the plating solution contains zinc sulfate, and the electrodeposition current density is 10 to 100mA cm -2 。
The preparation method according to the invention, wherein the electrodeposition time is 0 to 60 minutes.
In one embodiment of the preparation method of the invention, the method comprises the following steps:
1) Cutting commercial zinc foil and copper mesh into rectangles with certain sizes and the same size;
2) Pretreating the copper mesh obtained in the step 1) in an acid solution to remove a surface oxide layer;
3) Weighing a certain amount of analytically pure sodium sulfate, a certain amount of analytically pure zinc sulfate and a certain amount of analytically pure boric acid, dissolving in deionized water, and stirring in a beaker to form a uniformly dispersed colorless transparent solution serving as an electroplating solution;
4) And (3) taking the pretreated copper mesh obtained in the step (2) as a working electrode, taking the commercial zinc foil obtained in the step (1) as a counter electrode, performing controlled current electrodeposition treatment in the electroplating solution obtained in the step (3), and then drying to obtain a final product.
According to the above scheme of the invention, when a method for pre-depositing zinc metal layer with compact flaky stack and (002) crystal face orientation on the surface of three-dimensional copper net is carried out in the step 4), controlled current electrodeposition with the electrodeposition current density of 10-300mA cm is carried out -2 Preferably 10-100mA cm -2 The electrodeposition time is 0-60 minutes, preferably 540-720 seconds, and the zinc electrodeposition on the surface of the copper mesh can be realized.
And (3) directly taking the copper mesh as a working electrode, uniformly nucleating zinc metal on the surface of the copper mesh and performing oriented growth by controlling a current electrodeposition method, so that uniform oriented deposition of zinc metal on the surface of the copper mesh can be realized, and finally, the zinc metal pre-deposited layer with compact flaky stacking and (002) crystal face orientation is obtained. The zinc metal is fully covered on the surface of the copper net and uniformly distributed. The pre-deposited zinc layer with the surface morphology and (002) crystal face orientation characteristics can further induce uniform orientation deposition of zinc metal, so that the zinc cathode with the pre-deposited layer can reduce zinc dendrite generation and side reaction in the repeated charge and discharge process, thereby improving the cycle stability of the zinc cathode. Therefore, the three-dimensional composite zinc anode with the pre-deposited zinc layer is a zinc anode material with application prospect, and can be applied to anode materials of water-based zinc-based batteries, such as water-based zinc ion battery anode materials.
The electrodeposition method can be used for depositing a zinc metal layer with compact flaky stacking and (002) crystal face orientation on the surface of a three-dimensional conductive substrate with a porous structure, and the prepared three-dimensional composite material with the zinc layer with specific surface characteristics can be directly used as a zinc anode and applied to a water-based zinc-based battery, such as a water-based zinc ion battery.
The beneficial effects of the invention are as follows: the invention realizes the uniform deposition of zinc metal on the surface of the copper mesh in a few minutes by controlling the current electrodeposition, and the pre-deposited zinc layer has compact flaky stacking and surface characteristics of (002) crystal face orientation. The zinc cathode with the pre-deposition layer can further induce uniform orientation deposition of zinc metal, and reduce zinc dendrite generation and side reaction in the repeated charge and discharge process, thereby improving the cycle and rate performance of the zinc cathode. The invention has simple process and high preparation speed and meets the green chemical requirements. When the zinc-based zinc-ion battery cathode is used as a water-based zinc-ion battery cathode, compared with commercial zinc foil, the zinc-based zinc-ion battery cathode has obviously improved cycle stability and battery rate performance, and the electrodeposition method developed by the invention is proved to be applicable to pre-depositing a zinc layer with the specific surface characteristics on the surface of a three-dimensional substrate, so that the cycle and rate performance of the zinc cathode are improved. Meanwhile, the zinc layer with the specific surface characteristics is pre-deposited on the surface of the three-dimensional substrate with the porous structure, so that the obtained three-dimensional composite material is a zinc negative electrode capable of realizing excellent cycle and rate performance, and can be widely applied to large-scale, mobile portable, miniature or flexible wearable zinc-based batteries based on the zinc negative electrode.
Drawings
FIG. 1 is a schematic of electrodeposition of a pre-deposited zinc layer having a dense platelet morphology and (002) crystal plane orientation prepared in example 1 of the present invention;
FIG. 2 is a graph showing the copper mesh at 40mA cm in example 1 of the present invention -2 A scanning electron microscope image of zinc with different cut-off surface capacities is electrodeposited;
FIG. 3 is a graph showing the copper mesh at 40mA cm in example 1 of the present invention -2 Electrodeposit 6mAh cm -2 X-ray diffraction pattern of surface volume zinc;
FIG. 4 is a graph showing the copper mesh at 40mA cm in example 1 of the present invention -2 Electrodeposit 6mAh cm -2- X-ray photoelectron spectrum of zinc with surface capacity;
FIG. 5 shows a 2M ZnSO of a button symmetric cell based on the pre-deposited layer of zinc anode in example 1 of the invention 4 Circulation stability in aqueous electrolytes;
FIG. 6 shows a 2M ZnSO for a commercial zinc foil based button symmetric cell in example 1 of the present invention 4 Circulation stability in aqueous electrolytes;
FIG. 7 is a 2M ZnSO of a button symmetric cell of example 1 based on the pre-deposited layer of zinc anode of the invention 4 Scanning electron microscope pictures of the surface of the zinc cathode after 400h of testing in the water-based electrolyte;
FIG. 8 is a 2M ZnSO for a commercial zinc foil based button symmetric cell in example 1 of the present invention 4 Scanning electron microscope pictures of the surface of the zinc foil after 400h of testing in the water-based electrolyte;
FIG. 9 shows a 2M ZnSO for a zinc anode button cell based on the pre-deposited layer in example 6 of the invention 4 Circulation stability in aqueous electrolytes;
FIG. 10 shows a 2M ZnSO of a button symmetric cell based on a zinc anode of example 7 of the invention 4 Circulation stability in aqueous electrolytes.
Detailed Description
For a better understanding of the present invention, the present invention will be described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into rectangle of 1.2cm×1 cm;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) 15g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 40mA cm -2 The electrodeposition time is 540s, the working electrode is immediately taken out after the test, washed by deionized water and wiped by dust-free paper, and the three-dimensional composite material with compact flaky stacking morphology and (002) crystal face orientation of the pre-deposited zinc layer can be obtained.
Taking the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation as an example in the embodiment, a schematic diagram of the controlled-current electrodeposition of the present invention is shown in fig. 1. By applying a constant current in the acid electrolyte, dissolution of zinc will occur in commercial zinc foil and deposition of zinc will occur on the copper mesh surface. FIG. 2 is a copper mesh at 40mA cm -2 SEM images after constant current electrodeposition of zinc of different cut-off surface capacities. It can be seen that zinc is uniformly nucleated on the surface of the copper mesh during the initial phase of electrodeposition. With the capacity of the electrodeposited surface from 1mAh cm -2 Increase to 6mAh cm -2 The formed crystal nucleus grows into orderly arranged flaky shape and is densely and uniformly accumulated on the surface of the copper mesh. Phase analysis of the zinc anode after pre-deposition of the zinc layer (FIG. 3) revealed that after electrodeposition, a new derivative appearedThe peak was assigned to the Zn phase (PDF # 03-065-5973), indicating that zinc was deposited on the copper wire mesh with no by-product. As shown in fig. 4, zinc chemical bond analysis was further performed on the surface of the electrodeposited 540s composite material. No zinc-copper alloy was found to be produced during electrodeposition.
When the composite material of the pre-deposited zinc with compact flaky stacking morphology and (002) crystal face orientation prepared in the example is used as an electrode of a button symmetric battery, the area capacity is 1mAh cm -2 At 1mA cm -2 Is based on the button symmetric cell of the pre-deposited zinc cathode at 2M ZnSO 4 The aqueous electrolyte was allowed to stably circulate for 850h (FIG. 5). While button symmetric cells based on commercial zinc foil can only be cycled steadily for less than 100h under the same conditions (fig. 6). Proved by the method for pre-depositing the zinc layer, the circulating stability of the zinc cathode can be improved, so that the pre-deposited zinc cathode is a water-based zinc ion battery cathode material with application prospect.
We also performed morphological analysis of the electrode surface after cyclic testing. As shown in FIG. 7, the composite material was at 1mAh cm -2 And 1mA cm -2 After 400 hours of circulation under the condition of (2), no obvious dendrite growth is observed on the surface, and the morphology of flaky compact accumulation can be still observed; whereas commercial zinc foil has significant dishing and dendrite generation on its surface (fig. 8), which is responsible for the short circuit and failure of the symmetrical cell. Therefore, the electrodeposition method developed by the invention can be used for pre-depositing a zinc layer with (002) crystal face orientation and compact flaky stacking surface property on the surface of the three-dimensional copper mesh, so that the cycle stability of the zinc cathode is improved. Meanwhile, the zinc layer with (002) crystal face orientation and compact flaky stacking surface property is pre-deposited on the surface of the three-dimensional substrate with the porous structure, and the three-dimensional composite material is a zinc negative electrode capable of realizing excellent cycle stability, and can be applied to zinc-based batteries based on the zinc negative electrode, such as a water-based zinc ion battery.
Example 2
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into rectangle of 1.2cm×1 cm;
2) The copper net obtained in the step 1) is subjected to H with the mass fraction of 10 percent 2 SO 4 Pre-treating to remove the surface oxide layer;
3) 15g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 40mA cm -2 And taking out the working electrode immediately after the test, washing with deionized water and wiping with dust-free paper to obtain the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation.
Taking the composite material with compact flaky stacking morphology and (002) crystal face orientation of the pre-deposited zinc layer obtained in the example as an example, the symmetrical cell is assembled in 2M ZnSO 4 The cycle stability performance of the test in (a) was similar to that of example 1.
Example 3
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into rectangle of 1.2cm×1 cm;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 20% to remove a surface oxide layer;
3) 15g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. At CHI 760E electricityPerforming controlled current electrodeposition on a chemical workstation, wherein the current density is 40mA cm -2 And taking out the working electrode immediately after the test, washing with deionized water and wiping with dust-free paper to obtain the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation.
Taking the composite material with compact flaky stacking morphology and (002) crystal face orientation of the pre-deposited zinc layer obtained in the example as an example, the symmetrical cell is assembled in 2M ZnSO 4 The cycle stability performance of the test in (a) was similar to that of example 1.
Example 4
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into 2.4cm×2cm rectangle;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) 15g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 40mA cm -2 The capacity of the electrodeposited surface is 6mAh cm -2 And taking out the working electrode immediately after the test, washing with deionized water and wiping with dust-free paper to obtain the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation.
Taking the composite material with compact flaky stacking morphology and (002) crystal face orientation of the pre-deposited zinc layer obtained in the example as an example, the assembled symmetrical battery is manufactured in 2M ZnSO 4 The cycle stability performance of the test in (a) was similar to that of example 1.
Example 5
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into rectangle of 1.2cm×1 cm;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) Weighing 30g of analytically pure sodium sulfate, 30g of analytically pure zinc sulfate and 5g of analytically pure boric acid, dissolving in 200mL of deionized water, and stirring in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 40mA cm -2 The capacity of the electrodeposited surface is 6mAh cm -2 And taking out the working electrode immediately after the test, washing with deionized water and wiping with dust-free paper to obtain the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation.
Taking the composite material with compact flaky stacking morphology and (002) crystal face orientation of the pre-deposited zinc layer obtained in the example as an example, the assembled symmetrical battery is manufactured in 2M ZnSO 4 The cycle stability performance of the test in (a) was similar to that of example 1.
Example 6
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into rectangle of 1.2cm×1 cm;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) 15g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double-electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, and the copper mesh obtained in the step 1) is used as a working electrodeAs counter electrode, the colorless transparent solution obtained in step 3) was used as plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 10mA cm -2 And electrodepositing until a certain cut-off surface capacity is reached, immediately taking out the working electrode after testing, washing with deionized water, and wiping with dust-free paper to obtain the pre-deposited zinc layer.
Taking the composite material with the pre-deposited zinc layer obtained in the example as an example, when the capacity of the electrodeposited surface is 1mAh cm -2 When the copper mesh surface is pre-deposited with zinc layer, the copper mesh surface presents compact flaky stacking morphology and (002) crystal face orientation. The (002) and (100) crystal planes of this example were weaker in relative strength than example 1.
The sample obtained in this example was measured at 6mAh cm -2 Composite material of pre-deposited layer with cut-off surface capacity is taken as an example, and assembled symmetrical battery is manufactured by 2M ZnSO 4 The cycle stability performance of the test in (a) was slightly worse than that of example 1, but it was also able to stabilize the cycle for 350h (fig. 9).
Example 7
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into rectangle of 1.2cm×1 cm;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) 15g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 100mA cm -2 And electrodepositing until a certain cut-off surface capacity is reached, immediately taking out the working electrode after testing, washing with deionized water, and wiping with dust-free paper to obtain the pre-deposited zinc layer.
Taking the composite material with the pre-deposited zinc layer obtained in the example as an example, when the capacity of the electrodeposited surface is 1mAh cm -2 When the copper mesh surface pre-deposited zinc layer presents compact flaky stacking morphology and (002) crystal face orientation. When the capacity of the electrodeposited surface is increased to 3mAh cm -2 And 6mAh cm -2 Zinc particles grow into large particles. The (002) and (100) crystal planes of this example were weaker in relative strength than example 1.
The sample obtained in this example was measured at 6mAh cm -2 Composite material of pre-deposited layer with cut-off surface capacity is taken as an example, and assembled symmetrical battery is manufactured by 2M ZnSO 4 The cycle stability performance of the test in (a) was slightly inferior to that of example 1, but it was also able to stabilize the cycle for 350h (fig. 10).
Example 8
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh nickel screen into rectangle of 1.2cm×1 cm;
2) Pretreating the nickel screen obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) 15g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the nickel screen obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 40mA cm -2 The capacity of the electrodeposited surface is 6mAh cm -2 And taking out the working electrode immediately after the test, washing with deionized water and wiping with dust-free paper to obtain the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation.
Taking the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation obtained in the example as an example, the assembled symmetrical battery is prepared in 2M ZnSO 4 Cycle stability performance of the test in (1) and exampleSimilarly.
Example 9
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting a zinc sheet with the thickness of 1mm and a copper mesh with the size of 400 meshes into a rectangle with the thickness of 1.2cm multiplied by 1 cm;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) 15g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc sheet obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 40mA cm -2 The capacity of the electrodeposited surface is 6mAh cm -2 And taking out the working electrode immediately after the test, washing with deionized water and wiping with dust-free paper to obtain the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation.
Taking the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation obtained in the example as an example, the assembled symmetrical battery is prepared in 2M ZnSO 4 The cycle stability performance of the test in (a) was similar to that of example 1.
Example 10
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into rectangle of 1.2cm×1 cm;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) 15g of analytically pure sodium sulfate, 20g of analytically pure zinc acetate and 2.5g of analytically pure boric acid are weighed into 100mL of deionized water and stirred in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 40mA cm -2 The capacity of the electrodeposited surface is 6mAh cm -2 And taking out the working electrode immediately after the test, washing with deionized water and wiping with dust-free paper to obtain the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation.
Taking the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation obtained in the example as an example, the assembled symmetrical battery is prepared in 2M ZnSO 4 The cycle stability performance of the test in (a) was similar to that of example 1.
Example 11
The pre-deposited zinc layer of the present invention was prepared and characterized as follows:
1) Cutting 50 μm thick zinc foil and 400 mesh copper mesh into rectangle of 1.2cm×1 cm;
2) Pretreating the copper mesh obtained in the step 1) in HCl with the mass fraction of 10% to remove a surface oxide layer;
3) Weighing 30g of analytically pure sodium sulfate, 15g of analytically pure zinc sulfate and 20g of analytically pure indium sulfate, dissolving in 100mL of deionized water, and stirring in a beaker to form a uniformly dispersed colorless transparent solution as a plating solution;
4) In a standard double electrode device, the copper mesh obtained in the step 2) is directly used as a working electrode, the commercial zinc foil obtained in the step 1) is used as a counter electrode, and the colorless transparent solution obtained in the step 3) is used as a plating solution. Controlled current deposition was performed on a CHI 760E electrochemical workstation with a current density of 40mA cm -2 The capacity of the electrodeposited surface is 6mAh cm -2 And taking out the working electrode immediately after the test, washing with deionized water and wiping with dust-free paper to obtain the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation.
Taking the pre-deposited zinc layer with compact flaky stacking morphology and (002) crystal face orientation obtained in the example as an exampleSymmetrical cell in 2M ZnSO 4 The cycle stability performance of the test in (a) was similar to that of example 1.
Claims (12)
1. A battery negative electrode comprising a three-dimensional substrate and a zinc metal surface layer attached to the three-dimensional substrate, characterized in that the three-dimensional substrate has a three-dimensional porous structure, and the surface layer is a zinc layer mainly oriented by (002) crystal faces and densely stacked in a sheet shape.
2. The battery anode of claim 1, wherein the X-ray diffraction pattern of the zinc layer has strong characteristic peaks at 2Θ angles = 35-37 degrees.
3. The battery anode of claims 1-2, wherein the zinc layer is formed by an electrodeposition process.
4. The battery anode of claims 1-3, wherein the three-dimensional substrate is a copper mesh.
5. The battery anode of claims 1-4, which is a zinc metal anode for a zinc-based battery.
6. The method for producing a negative electrode for a battery according to claim 1, wherein a three-dimensional substrate is used as a working electrode, characterized in that the surface layer is formed on the three-dimensional substrate by an electrodeposition method in which a current is controlled.
7. The method of claim 6, wherein the electrodeposition current density is 10-300mA cm -2 。
8. The method of claims 6-7, wherein the three-dimensional substrate is an electrically conductive three-dimensional current collector made of a material selected from the group consisting of: metals, alloys, carbon materials, carbon composites.
9. The method of claims 6-8 wherein the plating solution used comprises a zinc salt selected from the group consisting of: zinc sulfate, zinc chloride, zinc trifluoromethane sulfonate, zinc bromide, zinc acetate.
10. The method of claim 9, wherein the plating solution used further comprises an additive selected from the group consisting of: sulfuric acid, boric acid, indium sulfate, phosphoric acid.
11. The method of claim 6, wherein the three-dimensional substrate is a copper mesh, the electroplating solution comprises zinc sulfate, and the electrodeposition current density is 10-100mA cm -2 。
12. The method of claim 10, wherein the electrodeposition time is 0 to 60 minutes.
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